Insertion reactions of small unsaturated molecules in the N–B bonds of boron guanidinates

Abstract

We report here 1,1- and 1,2-insertion reactions of small unsaturated molecules in the N–B bonds of two boron guanidinates, (Me₂N)C(NⁱPr)₂BCy₂ (1) and {ⁱPr(H)N}C(NⁱPr){N(p-^tBu-C₆H₄)}BCy₂ (2), and two bisboron guanidinates(2–), {ⁱPr(BCy₂)N}C(NⁱPr){N(p-^tBu-C₆H₄)}BCy₂ (3) and {ⁱPr(C₈H₁₄B)N}C(NⁱPr){N(p-Me-C₆H₄)}BC₈H₁₄ (4), the latter being prepared for the first time by double deprotonation of the corresponding guanidine with the 9-borabicyclo[3.3.1]nonane dimer, (H-BC₈H₁₄)₂. Compounds 1–4 easily insert aromatic isonitriles, XylNC (Xyl = 2,6-Me₂-C₆H₃) and (p-MeO-C₆H₄)NC, to give the expected diazaboroles 5–12, some of them being structurally characterised by X-ray diffraction. Interestingly, the BC₈H₁₄ derivatives 11 and 12 are in a fast temperature-dependent equilibrium with the de-insertion products, whose thermodynamic parameters are reported here. A correlation between these equilibria and the puckered heterocyclic structure found in the solid state for 11, and confirmed by DFT calculations, is also established. Reactions of the aforementioned guanidinates with CO are more sluggish or even precluded, and only one product, {ⁱPr(H)N}C{N(p-^tBu-C₆H₄)}(NⁱPr)(CO)BCy₂ (13), could be isolated in moderate yields. The 1,2-insertions of benzaldehyde in compounds 1, 2 and 4 are reversible reactions in all cases, and only one of the insertion products, {ⁱPr(H)N}C{N(p-^tBu-C₆H₄)}(NⁱPr)(PhHCO)BCy₂ (16a), was isolated and diffractrometrically characterised. Likewise, CO₂ reversibly inserts into a N–B bond of 2 to give {ⁱPr(H)N}C{N(p-^tBu-C₆H₄)}(NⁱPr)(CO₂)BCy₂ (19) with a conversion of ca. 9%. In all these equilibria, de-insertion is always favoured upon increasing the temperature.